EP0235722B1 - Propargyl cinnamates, process for their production and their application in pest control - Google Patents

Propargyl cinnamates, process for their production and their application in pest control Download PDF

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Publication number
EP0235722B1
EP0235722B1 EP87102557A EP87102557A EP0235722B1 EP 0235722 B1 EP0235722 B1 EP 0235722B1 EP 87102557 A EP87102557 A EP 87102557A EP 87102557 A EP87102557 A EP 87102557A EP 0235722 B1 EP0235722 B1 EP 0235722B1
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carbon atoms
propargyl
formula
cinnamate
substituted
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German (de)
French (fr)
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EP0235722A1 (en
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Wolfgang Dr. Seppelt
Hans-Juergen Dr. Neubauer
Heinrich Dr. Adolphi
Peter Dr. Hofmeister
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BASF SE
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/10—Aromatic or araliphatic carboxylic acids, or thio analogues thereof; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
    • A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
    • A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
    • C07C69/618—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety having unsaturation outside the six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/62—Halogen-containing esters
    • C07C69/65—Halogen-containing esters of unsaturated acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/734—Ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/734—Ethers
    • C07C69/736—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring

Definitions

  • alkyl esters of alkynic acids or alkynyl esters are suitable for controlling mites (US Pat. No. 4,024,278 or US Pat. No. 3,996,380). However, the effect is limited to arachnids.
  • the invention thus relates to the new cinnamic acid propargyl esters of the formula with the proviso that the radicals R1 to R5 are not all hydrogen at the same time, processes for the preparation of these compounds and agents which contain the above-mentioned cinnamic acid propargyl esters 1 as active ingredient.
  • esters of the formula I can be obtained by reacting corresponding cinnamic acids (II) with propargyl alcohol (cf. Houben-Weyl, Methods of Organic Chemistry, Volume VIII, page 516 ff. Georg-Thieme-Verlag, Stuttgart 1952).
  • the reaction can be shifted in a manner known per se by adding catalysts such as sulfuric acid, hydrogen halide, sulfonic acid, acidic ion exchangers and the esterification equilibrium by withdrawing the water or the ester I from the reaction mixture, e.g. by azeotropic distillation or by binding the water to sulfuric or hydrohalic acid.
  • catalysts such as sulfuric acid, hydrogen halide, sulfonic acid, acidic ion exchangers and the esterification equilibrium by withdrawing the water or the ester I from the reaction mixture, e.g. by azeotropic distillation or by binding the water to sulfuric or hydrohalic acid.
  • Suitable acid binders are the customary basic agents, in particular aliphatic, aromatic and heterocyclic amines, for example triethylamine, dimethylamine, piperidine, diazabicytlooctane, dimethylaniline, dimethylbenzylamine, pyridine, lutidine, dimethylaminopyridine.
  • Alkali metal carbonates such as sodium or potassium carbonate, are also suitable as acid acceptors.
  • the reaction can be carried out in a solvent or diluent.
  • the acid acceptors mentioned themselves or the following solvents or diluents or mixtures thereof are partially suitable for this purpose:
  • Aliphatic and aromatic, optionally chlorinated hydrocarbons such as petroleum ether, benzene, toluene, xylene, gasoline, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloromethane, chlorobenzene, ethers such as diethyl and di-n-butyl ether, methyl tert-butyl ether , Tetrahydrofuran, dioxane; Ketones, for example acetone, methyl ethyl ketone, methyl isopropyl ketone; also nitriles such as acetonitrile and propionitrile.
  • hydrocarbons such as petroleum ether, benzene, toluene, xylene, gasoline, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloromethane, chlorobenzene, ethers such as diethyl and di-n-butyl ether,
  • the starting materials are usually used in a stoichiometric ratio. However, an excess of one or the other can be advantageous in individual cases.
  • the reaction usually proceeds at a sufficient rate above 0 ° C. Since it mostly develops under heat, it can be advantageous to provide a cooling option.
  • the cinnamic acid proparyl esters according to the invention can also be prepared by practically all known methods of ester synthesis, for example by reacting corresponding cinnamic acid anhydrides (cf. see Houben-Weyl aa 0., pp. 508 to 628; C. Ferri, Reactions of Organic Synthesis, pp. 446 ff., Georg-Thieme-Verlag, Stuttgart 1978; S. Patai, The Chemistry of Carboxylic Acids and Esters , Pp. 505 ff., Intercience Publishers, London 1969), or for example from substituted aromatic aldehydes by condensation with the suitably activated acetic acid ester (see J. Org. Chem. Of USSR (1970), 2309).
  • the cinnamic acids required as starting material are either known and in some cases commercially available, or they can be prepared by generally known chemical processes (see Methodicum Chimicum, Georg Thieme Verlag, Stuttgart 1975; Vol. 5, pp. 573 ff. Or, for example, Organic Reaction, John Wiley and Sons, New York 1967, vol. 15, p. 204 ff).
  • the cinnamic acid chlorides made from them in some cases were e.g. T. to Houben-Weyl a. a. Obtained p. 463 ff.
  • the female moths lay their eggs in closed groups on parchment paper. Cut paper strips carrying approx. 200 - 300 eggs are immersed in the aqueous preparation of the active ingredient for about 5 seconds 2 days after being deposited (concentration information in g active ingredient per 100 g solution). Then place them in a petri dish ( 0 10 cm) on moist cellulose.
  • the evaluation takes place after hatching of the untreated control test, i.e. after 5 to 6 days.
  • Stick-on labels are stuck to the top with pieces of adhesive tape (approx. 0.8 cm).
  • the eggs collected in a container are attached to the adhesive strip edge by immersing the labels in the container.
  • the eggs are immersed in the aqueous active ingredient preparation for about 5 seconds and drained onto filter paper.
  • the eggs should not be laid on the paper.
  • the cut labels are placed in plastic pallets with adhesive strips facing up. Half a cotton roll soaked in water is placed in the cup to prevent drying out and the pallet is covered with a glass plate.

Abstract

1. A propargyl cinnamate of the formula (I) see diagramm : EP0235722,P6,F3 where R**1 , R**2 , R**3 , R**4 and R**5 are identical or different and independently of one another are each H, F, Cl, Br, branched or straight-chain alkyl or alkenyl of not more than 4 carbon atoms or alkoxy or alkenyloxy of not more than 4 carbon atoms, which may each be substituted by halogen, and R**2 and R**3 together may form the moiety -O-CH2 -O-, or are each phenyl or phenoxy which may be substituted in the 3- and/or 4-position by halogen, alkyl or alkoxy of not more than 3 carbon atoms or by the moiety -O-CH2 -O-, with the proviso that R**1 to R**5 are not all simultaneously hydrogen.

Description

Es ist bekannt, daß Alkylester von Alkinsäuren oder Alkinylester geeignet sind zur Bekämpfung von Milben (US 4 024 278 bzw. US 3 996 380). Die Wirkung ist jedoch auf Arachniden beschränkt.It is known that alkyl esters of alkynic acids or alkynyl esters are suitable for controlling mites (US Pat. No. 4,024,278 or US Pat. No. 3,996,380). However, the effect is limited to arachnids.

In Journal of Organic Chemistry, Band 44, 1979, Z. 4524- 4527, werden polarographische Untersuchungen am unsubstituierten trans-Zimtsäurepropargylester beschrieben.In Journal of Organic Chemistry, Volume 44, 1979, lines 4524-4527, polarographic investigations on the unsubstituted trans-cinnamic acid propargylester are described.

Es wurde gefunden, daß Zimtsäurepropargylester der Formel

Figure imgb0001
in der Rj, R2, R3, R4 und Rs gleich oder verschieden sind und unabhängig voneinander stehen für H, F, CI, Br, verzweigtes oder unverzweigtes Alkyl oder Alkenyl mit bis zu 4 Kohlenstoffatomen, Alkoxy oder Alkenyloxy mit bis zu 4 Kohlenstoffatomen, die durch Halogenatome substituiert sein können, wobei R2 und R3 gemeinsam den Molekülanteil ―O―CH2―O― bilden können, und für Phenyl oder Phenoxy, das in 3-und/oder 4-Stellung durch Halogen, Alkyl und Alkoxy mit bis zu 3 Kohlenstoffatomen oder durch den Molekülteil ―O―CH2―O substituiert sein kann, insektizid, akarizid und besonders ovizid bzw. ovolarvizid sehr gut wirksam und bekannten Wirkstoffen ähnlicher Struktur bzw. gleicher Wirkungsrichtung überlegen sind.It has been found that propargyl cinnamic acid of the formula
Figure imgb0001
 in which R j , R 2 , R3, R4 and Rs are identical or different and independently of one another are H, F, CI, Br, branched or unbranched alkyl or alkenyl having up to 4 carbon atoms, alkoxy or alkenyloxy having up to 4 carbon atoms which can be substituted by halogen atoms, where R 2 and R3 together can form the molecular moiety ―O ― CH 2 ―O―, and for phenyl or phenoxy which is in the 3 and / or 4 position by halogen, alkyl and alkoxy up to 3 carbon atoms or can be substituted by the molecular part ―O ― CH 2 ―O, insecticidal, acaricidal and especially ovicidal or ovolarvicidal are very effective and are superior to known active substances of similar structure or the same direction of action.

Gegenstand der Erfindung sind somit die neuen Zimtsäurepropargylester der Formel mit der Maßgabe, daß die Reste R1 bis R5 nicht alle gleichzeitig Wasserstoff bedeuten, Verfahren zur Herstellung dieser Verbindungen sowie Mittel, die die oben genannten Zimtsäurepropargylester 1 als Wirkstoff enthalten.The invention thus relates to the new cinnamic acid propargyl esters of the formula with the proviso that the radicals R1 to R5 are not all hydrogen at the same time, processes for the preparation of these compounds and agents which contain the above-mentioned cinnamic acid propargyl esters 1 as active ingredient.

Die Ester der Formel I können durch Umsetzung entsprechender Zimtsäuren (II) mit Propargylalkohol erhalten werden (vgl. Houben-Weyl, Methoden der organischen Chemie, Band VIII, Seite 516 ff. Georg-Thieme-Verlag, Stuttgart 1952).The esters of the formula I can be obtained by reacting corresponding cinnamic acids (II) with propargyl alcohol (cf. Houben-Weyl, Methods of Organic Chemistry, Volume VIII, page 516 ff. Georg-Thieme-Verlag, Stuttgart 1952).

Die Umsetzung kann in an sich bekannter Weise durch Zusatz von Katalysatoren wie Schwefelsäure, Halogenwasserstoff, Sulfonsäure, sauren Ionenaustauschern und das Veresterungsgleichgewicht in gewünschtem Sinne verschoben werden, indem man dem Reaktionsgemisch das Wasser oder den Ester I entzieht, z.B. durch azeotrope Destillation oder durch Bindung des Wassers an Schwefel- oder Halogenwasserstoffsäure.The reaction can be shifted in a manner known per se by adding catalysts such as sulfuric acid, hydrogen halide, sulfonic acid, acidic ion exchangers and the esterification equilibrium by withdrawing the water or the ester I from the reaction mixture, e.g. by azeotropic distillation or by binding the water to sulfuric or hydrohalic acid.

Ebensogut kann man die entsprechenden Säurehalogenide 111, in denen Hal(ogen) für Fluor, Chlor und Brom steht, mit Propargylalkohol in Gegenwart eines Säureacceptors umsetzen (vgl. Houben-Weyl, Methoden der organischen Chemie, Band VIII, S. 543 ff., Georg-Thieme-Verlag, Stuttgart 1952).

Figure imgb0002
Als Säurebindemittel eignen sich die üblichen basischen Mittel, insbesondere aliphatische, aromatische und heterocylische Amine, z.B. Triethylamin, Dimethylamin, Piperidin, Diazabicytlooctan, Dimethylanilin, Dimethylbenzylamin, Pyridin, Lutidin, Dimethylaminopyridin. Auch Alkalimetallcarbonate, wie Natrium-oder Kaliumcarbonat eignen sich als Säureacceptoren.The corresponding acid halides 111, in which Hal (above) represents fluorine, chlorine and bromine, can just as well be reacted with propargyl alcohol in the presence of an acid acceptor (cf. Houben-Weyl, Methods of Organic Chemistry, Volume VIII, p. 543 ff., Georg Thieme Verlag, Stuttgart 1952).
Figure imgb0002
 Suitable acid binders are the customary basic agents, in particular aliphatic, aromatic and heterocyclic amines, for example triethylamine, dimethylamine, piperidine, diazabicytlooctane, dimethylaniline, dimethylbenzylamine, pyridine, lutidine, dimethylaminopyridine. Alkali metal carbonates, such as sodium or potassium carbonate, are also suitable as acid acceptors.

Die Umsetzung kann in einem Lösungs- oder Verdünnungsmittel ausgeführt werden. Hierzu sind teilweise die angeführten Säureacceptoren selbst oder beispielsweise folgende Lösungs- oder Verdünnungsmittel oder Gemische derselben geeignet:The reaction can be carried out in a solvent or diluent. The acid acceptors mentioned themselves or the following solvents or diluents or mixtures thereof are partially suitable for this purpose:

Aliphatische und aromatische, gegebenenfalls chlorierte Kohlenwasserstoffe, wie Petrolether, Benzol, Toluol, Xylol, Benzin, Dichlormethan, Chloroform, Tetrachlormethan, 1,2-Dichlormethan, Chlorbenzol, Ether wie Diethyl- und Di-n-butylether, Methyl-tert.-butylether, Tetrahydrofuran, Dioxan; Ketone beispielsweise Aceton, Methylethylketon, Methylisopropylketon; ferner Nitrile wie Acetonitril und Propionitril.Aliphatic and aromatic, optionally chlorinated hydrocarbons, such as petroleum ether, benzene, toluene, xylene, gasoline, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloromethane, chlorobenzene, ethers such as diethyl and di-n-butyl ether, methyl tert-butyl ether , Tetrahydrofuran, dioxane; Ketones, for example acetone, methyl ethyl ketone, methyl isopropyl ketone; also nitriles such as acetonitrile and propionitrile.

Üblicheweise setzt man die Ausgangsstoffe in stöchiometrischem Verhältnis ein. Ein Überschuß des einen oder anderen kann in Einzelfällen aber durchaus vorteilhaft sein.The starting materials are usually used in a stoichiometric ratio. However, an excess of one or the other can be advantageous in individual cases.

Die Umsetzung verläuft gewöhnlich oberhalb 0°C mit ausreichender Geschwindigkeit. Da sie meist unter Wärmeentwicklung verläuft, kann es von Vorteil sein, eine Kühlmöglichkeit vorzusehen.The reaction usually proceeds at a sufficient rate above 0 ° C. Since it mostly develops under heat, it can be advantageous to provide a cooling option.

Die erfindungsgemäßen Zimtsäureproparylester können außerdem noch nach praktisch allen bekannten Verfahren der Estersynthese hergestellt werden, beispielsweise durch Umsetzung von entsprechenden Zimtsäureanhydriden (vgl. Houben-Weyl a. a. O., S. 478) mit Propargylalkohol, durch Umsetzung von entsprechenden Zimtsäuresalzen mit Propargylhalogeniden, durch Umesterungsreaktionen (vgl. Houben-Weyl a. a. 0., S. 508 bis 628; C. Ferri, Reaktionen der organischen Synthese, S. 446 ff., Georg-Thieme-Verlag, Stuttgart 1978; S. Patai, The Chemistry of Carboxylic Acids and Esters, S. 505 ff., lnterscience Publishers, London 1969), oder beispielsweise aus substituierten aromatischen Aldehyden durch Kondensation mit dem geeignet aktivierten Essigsäureester (s. J. Org. Chem. of USSR (1970), 2309).The cinnamic acid proparyl esters according to the invention can also be prepared by practically all known methods of ester synthesis, for example by reacting corresponding cinnamic acid anhydrides (cf. see Houben-Weyl aa 0., pp. 508 to 628; C. Ferri, Reactions of Organic Synthesis, pp. 446 ff., Georg-Thieme-Verlag, Stuttgart 1978; S. Patai, The Chemistry of Carboxylic Acids and Esters , Pp. 505 ff., Intercience Publishers, London 1969), or for example from substituted aromatic aldehydes by condensation with the suitably activated acetic acid ester (see J. Org. Chem. Of USSR (1970), 2309).

Die als Ausgangsmaterial benötigten Zimtsäuren sind entweder bekannt und teilweise handelsüblich, oder lassen sich nach allgemein bekannten chemischen Verfahren herstellen (s. Methodicum Chimicum, Georg Thieme Verlag, Stuttgart 1975; Bd. 5, S. 573 ff. oder z.B. Organic Reaktions, John Wiley and Sons, New York 1967, Vol. 15, p. 204 ff). Die aus ihnen in einigen Fällen hergestellten Zimtsäurechloride wurden z. T. nach Houben- Weyl a. a. O. S. 463 ff. erhalten.The cinnamic acids required as starting material are either known and in some cases commercially available, or they can be prepared by generally known chemical processes (see Methodicum Chimicum, Georg Thieme Verlag, Stuttgart 1975; Vol. 5, pp. 573 ff. Or, for example, Organic Reaction, John Wiley and Sons, New York 1967, vol. 15, p. 204 ff). The cinnamic acid chlorides made from them in some cases were e.g. T. to Houben-Weyl a. a. Obtained p. 463 ff.

Die Herstellung aller erfindungsgemäßen Verbindungen der Formel (I) ist durch entsprechende Abwandlung des folgenden Beispiels möglich:

  • Beispiel
All compounds of the formula (I) according to the invention can be prepared by modifying the following example accordingly:
  • example

12,0 g 2-Methoxy-Zimtsäurechlorid in 30 ml Tetrahydrofuran werden mit 3,75 g Propargylalkohol versetzt und unter Eiskühlung 20 ml Pyridin zugetropft. Man rührt 8 h beim Raumtemperatur, filtriert und engt i.V. ein. Der Rückstand wird in 80 ml Essigester aufgenommen, zweimal mit 10 %iger HCI und zweimal mit Wasser gewaschen. Man trocknet über Na2S04 und zieht das Lösungsmittel im Vakuum ab. Der Rückstand wird säulenchromatographisch (Hexan: Essigester 1 : 1) gereinigt. Nach Entfernen des Laufmittels verbleiben 9,9 g des 2-Methoxy-Zimsäurepropargylester als weißes Pulver. FP. 84 bis 870C Ausbeute: 9,9 g (75 % d. ber. Menge) Analyse: Ber. C 72,2H 5.6 Gef. C 72.3H 5.9

  • IH-NMR (CDCI3, 300 MHz): 8.03 d (1 H); 7.50 d (1 H); 7.35 t (1 H); 6.90 m (2H); 6.58 d (1 H); 4.80 sd (2H); 3.90 s (3H); 2.50 st (4H).
3.75 g of propargyl alcohol are added to 12.0 g of 2-methoxy-cinnamic acid chloride in 30 ml of tetrahydrofuran and 20 ml of pyridine are added dropwise while cooling with ice. The mixture is stirred for 8 h at room temperature, filtered and concentrated in vacuo. The residue is taken up in 80 ml of ethyl acetate, washed twice with 10% HCl and twice with water. It is dried over Na 2 S0 4 and the solvent is removed in vacuo. The residue is purified by column chromatography (hexane: ethyl acetate 1: 1). After the eluent has been removed, 9.9 g of the 2-methoxycimic acid propargylester remain as a white powder. FP. 84 to 870C Yield: 9.9 g (75% of calculated amount) Analysis: calc. C 72.2H 5.6 Found C 72.3H 5.9
  • I H -NMR (CDCI 3 , 300 MHz): 8.03 d (1 H); 7.50 d (1H); 7.35 t (1H); 6.90 m (2H); 6.58 d (1H); 4.80 sd (2H); 3.90 s (3H); 2.50 st (4H).

Die in der nachstehenden Tabelle mit physikalischen Angaben (Brechungsindex, nD oder Fp., OC) versehenen Wirkstoffe wurden durch sinngemäße Abwandlung der vorstehenden Vorschrift aus entsprechenden Vorprodukten erhalten; die nicht näher charakterisierten Verbindungen lassen sich auf einem der vorstehend angegebenen Wege erhalten; sie lassen eine vergleichbare biologische Wirkung erwarten.

Figure imgb0003
Figure imgb0004
Figure imgb0005
In den nachstehenden Beispielen zur biologischen Wirkung wurde die aus der US-PS 3 996 380 bekannte Verbindung
Figure imgb0006
als Vergleichsmittel gewählt.The active substances provided in the table below with physical details (refractive index, n D or Fp., O C) were obtained from corresponding preliminary products by appropriate modification of the above regulation; the compounds not characterized in more detail can be obtained in one of the ways indicated above; they are expected to have a comparable biological effect.
Figure imgb0003
Figure imgb0004
Figure imgb0005
 In the biological activity examples below, the compound known from US Pat. No. 3,996,380 was used
Figure imgb0006
 chosen as a means of comparison.

Prodenia litura (Ägypt. Baumwollwurm), Wirkung auf EiablagenProdenia litura (Egyptian cottonworm), effect on egg laying

Die weiblichen Falter legen ihre Eier in geschlossenen Gruppen auf Pergamentpapier ab. Ausgeschnittene Papierstreifen, die ca. 200 - 300 Eier tragen, werden 2 Tage nach der Ablage ca. 5 Sekunden in die wäßrige Wirkstoffaufbereitung getaucht (Konzentrationsangaben in g Wirkstoff je 100 g Lösung). Anschließend legt man sie in eine Petrischale (0 10 cm) auf feuchten Zellstoff.The female moths lay their eggs in closed groups on parchment paper. Cut paper strips carrying approx. 200 - 300 eggs are immersed in the aqueous preparation of the active ingredient for about 5 seconds 2 days after being deposited (concentration information in g active ingredient per 100 g solution). Then place them in a petri dish ( 0 10 cm) on moist cellulose.

Die Auswertung erfolgt nach dem Schlüpfen des unbehandelten Kontrollversuches, d.h. nach 5 bis 6 Tagen.The evaluation takes place after hatching of the untreated control test, i.e. after 5 to 6 days.

Als wirksam werden die Proben eingestuft, bei denen kein Raupenschlupf erfolgt. Treten vereinzelte Räupchen auf, bewerten wir dieses als Grenze der Wirksamkeit.

  • Beispiel 2 0,02% ca. 80% Mortalität 6 0,04% ca. 80% Mortalität 28 0,02% ca. 100% Mortalität
  • Vergleichsmittel 0,1% ca. 45% Mortalität
Samples without caterpillar slippage are classified as effective. If isolated caterpillars appear, we rate this as the limit of effectiveness.
  • Example 2 0.02% approx. 80% mortality 6 0.04% approx. 80% mortality 28 0.02% approx. 100% mortality
  • Comparative mean 0.1% approx. 45% mortality

Dysdercus intermedius (Baumwollwanze), Ovizide WirkungDysdercus intermedius (cotton bug), ovicidal activity

Stecketiketten werden am oberen Rand mit Klebestreifenstücken (ca. 0, 8 cm) beklebt.Stick-on labels are stuck to the top with pieces of adhesive tape (approx. 0.8 cm).

24 Stunden vor Versuchsbeginn werden die in einem Gefäß gesammelten Eier durch Eintauchen der Etiketten in das Gefäß an dem Klebestreifenrand befestigt.24 hours before the start of the experiment, the eggs collected in a container are attached to the adhesive strip edge by immersing the labels in the container.

Die Eier werden für ca. 5 Sekunden in die wäßrige Wirkstoffaufbereitung getaucht und auf Filterpapier abgetropft. Dabei sollen die Eier nicht auf das Papier gelegt werden.The eggs are immersed in the aqueous active ingredient preparation for about 5 seconds and drained onto filter paper. The eggs should not be laid on the paper.

Die zurechtgeschnittenen Etiketten werden in Plastikpaletten gestellt, Klebestreifen nach oben. Eine halbe mit Wasser durchfeuchtete Watterolle wird in den Becher gelegt, um Austrocknung zu vermeiden und die Palette mit einer Glasplatte abgedeckt.The cut labels are placed in plastic pallets with adhesive strips facing up. Half a cotton roll soaked in water is placed in the cup to prevent drying out and the pallet is covered with a glass plate.

Nach ca. 8 Tagen wird bonitiert (bei der Kontrolle müssen die Larven geschlüpft sein).After approx. 8 days, a rating is made (the larvae must have hatched during the control).

In diesem Versuch waren beispielsweise die Verbindungen 2, 5, 8, 13, 14, 21, 27, 28 besser als das Vergleichsmittel.In this experiment, for example, compounds 2, 5, 8, 13, 14, 21, 27, 28 were better than the comparative agent.

Claims (6)

1. A propargyl cinnamate of the formula (I)
Figure imgb0009
where R1, R2, R3, R4 and R5 are identical or different and independently of one another are each H, F, Cl, Br, branched or straight-chain alkyl or alkenyl of not more than 4 carbon atoms or alkoxy or alkenyloxy of not more than 4 carbon atoms, which may each be substituted by halogen, and R2 and R3 together may form the moiety ―O―CH2―O―, or are each phenyl or phenoxy which may be substituted in the 3- and/or 4-position by halogen, alkyl or alkoxy of not more than 3 carbon atoms or by the moiety -0-CH2-O~, with the proviso that R1 to R5 are not all simultaneously hydrogen.
2. A process for the preparation of a propargyl cinnamate of the formula I as claimed in claim 1, wherein an appropriate cinnamic acid or its acyl halide is reacted with propargyl alcohol, in the presence or absence of an acid acceptor.
3. A pesticide containing a propargyl cinnamate of the formula (I)
Figure imgb0010
where Ri, R2, R3, R4 and R5 are identical or different and independently of one another are each H, F, Cl, Br, branched or straight-chain alkyl or alkenyl of not more than 4 carbon atoms or alkoxy or alkenyloxy of not more than 4 carbon atoms, which may each be substituted by halogen, and R2 and R3 together may form the moiety ―O―CH2―O―, or are each phenyl or phenoxy which may be substituted in the 3- and/or 4-position by halogen, alkyl or alkoxy of not more than 3 carbon atoms or by the moiety ―O―CH2― O-.
4. A pesticide containing a solid or liquid carrier and one or more cinnamates of the formula I as claimed in claim 3.
5. Use of a cinnamate of the formula I as claimed in claim 3 as an insecticide, acaricide or, in particular, ovicide.
6. A method of controlling pests, wherein an effective amount of the cinnamate of the formula I as claimed in claim 3 is allowed to act on pests or their habitat.
EP87102557A 1986-02-26 1987-02-24 Propargyl cinnamates, process for their production and their application in pest control Expired EP0235722B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87102557T ATE45723T1 (en) 1986-02-26 1987-02-24 CINNAID PROPARGYL ESTER, PROCESS FOR THEIR PRODUCTION AND USE FOR PEST CONTROL.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863606168 DE3606168A1 (en) 1986-02-26 1986-02-26 Cinnamic acid propargyl esters, process for their preparation and their use for pest control
DE3606168 1986-02-26

Publications (2)

Publication Number Publication Date
EP0235722A1 EP0235722A1 (en) 1987-09-09
EP0235722B1 true EP0235722B1 (en) 1989-08-23

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Country Status (4)

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EP (1) EP0235722B1 (en)
JP (1) JPS62205046A (en)
AT (1) ATE45723T1 (en)
DE (2) DE3606168A1 (en)

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Publication number Priority date Publication date Assignee Title
JPH07103001B2 (en) * 1989-10-19 1995-11-08 高砂香料工業株式会社 Acaricide
DE4124989A1 (en) * 1991-07-27 1993-02-04 Basf Ag (BETA) -SUBSTITUTED CINNAMENT DERIVATIVES
US5405989A (en) * 1992-11-10 1995-04-11 Sumitomo Chemical Co., Ltd. Propargyl ester compounds, acaricides containing the same as an active ingredient and an acaricidal method
SE0003026D0 (en) * 2000-08-25 2000-08-25 Kerstin Sunnerheim Use for conifer sapling protection

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DE2210633C2 (en) * 1972-03-06 1983-09-22 Bayer Ag, 5090 Leverkusen Condensed pyridine derivatives, processes for their preparation and pharmaceuticals containing these compounds
DE2735856A1 (en) * 1977-08-09 1979-02-22 Klinge Co Chem Pharm Fab NEW 1,3-DIPHENOXYPROPAN-2-ON DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS MEDICINAL PRODUCTS
CA1116622A (en) * 1978-03-15 1982-01-19 Yasuhiro Morisawa Iodopropargyl derivatives their use and preparation
DE3230775A1 (en) * 1982-08-19 1984-02-23 Consortium für elektrochemische Industrie GmbH, 8000 München Aryl fatty acid propargyl esters, their preparation and use as insecticides
US4812161A (en) * 1984-08-08 1989-03-14 Nippon Soda Co., Ltd. Thia (oxa) diazole derivatives

Also Published As

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ATE45723T1 (en) 1989-09-15
JPS62205046A (en) 1987-09-09
DE3606168A1 (en) 1987-08-27
EP0235722A1 (en) 1987-09-09
DE3760475D1 (en) 1989-09-28

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